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  • 1
    Electronic Resource
    Electronic Resource
    Reduktive Arylierung von Vinyl-trifluoromethansulfonaten durch Friedel-Crafts-Reaktion (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1255-1256 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reductive Arylation of Vinyl Trifluromethanesulfonates by Friedel-Crafts ReactionThe reaction of vinyl triflates 1 with benzene and toluene in the presence of aluminium trichloride gives alkyl-, alkenyl-, and 1,1-diarylalkanes 5, 6, 3, 9 depending on the structure of the substrate used. A mechanism for the reductive arylation is proposed.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200724
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  • 2
    Electronic Resource
    Electronic Resource
    Study on the System CoSeO4—NiSeO4—H2O at 30°C Crystal Structure of CoSeO4 · 5 H2O (1985)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 528 (1985), S. 183-190 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Das System CoSeO4-NiSeO4—H2O bei 30°C. Kristallstruktur des CoSeO4 · 5 H2OEs wird das System CoSeO4—NiSeO4—H2O bei 30°C untersucht. Die Kristallwerden aus wäßriger Lösung durch langsames Eindampfen erhalten. Die gefundenen Phasen sind CoSeO4 · 5 H2O und NiSeO4 · 6 H2O; CoSeO4 · 6 H2O wird dann gefunden, wenn die Kristallisation der Co-Verbindung in Gegenwart von Ni erfolgt. Diese drei Phasen zeigen einen begrenzten Ersatz des Metalls auf Grund von Röntgenpulverdaten. Die Kristallstruktur des CoSeO4 · 5 H2O ist triklin, a = 6.435(1), b = 10,703(2), c = 6,220(1) Å, α = 98,71(1), β = 109,60(2), γ = 75,54(1)°, P1, Z = 2. Verfeinerung bis zu R = 0,032 für alle beobachteten Reflexe. Die Kristallstruktur ist isostrukturell zu CuSO4 · 5 H2O und besteht aus Ketten von Co(H2O)4-Ionen parallel zu [110], die brückengebunden über die SeO4-Anionen sind. Das fünfte Wassermolekül wirkt als Puffer.
    Notes: A study of the system CoSeO4—NiSeO4—H2O at 30°C has been carried out. Crystals were obtained by slow evaporation from a water solution. The identified phases were CoSeO4 · 5 H2O and NiSeO4 · 6 H2O, but CoSeO4 · 6 H2O is identified when the crystallization of Co compound is carried out in presence of Ni. The three phases show a limited replacement of metal according to X-ray powder results. The crystal structure of CoSeO4 · 5 H2O has been solved, the come pound is triclinic, a = 6.435(1), b = 10.703(2), c = 6.220(1) Å, α = 98.71(1), β = 109.60(2), γ = 75.54(1)°, P1, Z = 2. Refinement was terminated at R = 0.035 for all observed reflections. The crystal structure is isostructural to CuSO4 · 5 H2O and consists of Co(H2O)4 ions chains parallel to [110] μ-linked by the SeO4. The fifth water molecule acts as buffer.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19855280921
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  • 3
    Electronic Resource
    Electronic Resource
    Complexes of IIB Metal Halides with N,N-Diethylbenzenecarbothioamide crystal structure of [Hg{C6H5C(S)N(C2H5)2}I2]2 (1986)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 539 (1986), S. 219-228 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Komplexe von IIB Metall-halogeniden mit N,N-Diethylbenzocarbothioamiden. Kristallstruktur von [Hg{C6H5C(S)N(C2H5)2}I2]2Verschiedene Komplexe von N,N-Diethylbenzocarbothioamide (DEBCTA) mit MX2 (M = Zn, Cd oder Hg und X = Cl, Br oder I) wurden hergestellt und mittels Elementaranalyse, Molgewichtsbestimmung, IR, 1H-NMR-Spektren und konduktometrischen Messungen untersucht. Die Kristallstruktur von [Hg(DEBCTA)I2]2 wurde mit Hilfe von Röntgenbeugungsdaten ermittelt (2402 beobachtete unabhängige Reflexe, R = 0,097). [Hg(DEBCTA)I2]2 kristallisiert monoklin in der Raumgruppe P21/n mit zwei Formeleinheiten pro Elementarzelle; Gitterkonstanten a = 1383,9(2), b = 834,3(1), c = 1 418,1(2) pm, β = 101,03(1)°. Im dimeren Komplex sind die verzerrt-tetraedrisch koordinierten Hg-Atome von je einem S-Atom des Liganden, einem terminalen I-Atom und zwei verbrückenden I-Atomen umgeben.
    Notes: Complexes having the empirical formulae M(DEBCTA)2X2 (M = Zn or Cd, X = Br or I, DEBCTA = N,N-diethylbenzenecarbothioamide), Zn(DEBCTA)Cl2, Cd2(DEBCTA)Cl4 and Hg(DEBCTA)X2 (X = Cl, Br or I) were made by reaction of zinc, cadmium or mercury dihalides in ethanol or 1,2-dichloroethane. All complexes have been characterized by elemental analysis, conductance and molecular weight measurements and by infrared and 1H-NMR spectral studies. In addition, the structure of [Hg(DEBCTA)I2]2 has been determined by single-crystal X-ray crystallography and refined to a conventional R factor of 0.097. The compound crystallizes in the monoclinic space group P21/n with a = 1383.9(2), b = 834.3(1), c = 1418.2(2) pm, β = 101.03(1)° and Z = 2. The molecule was found to have a dimeric structure involving two asymmetrical iodine bridges in which the Hg atom lies a tetrahedral environment and the ligands lie mutually trans with respect to one another.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19865390823
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  • 4
    Electronic Resource
    Electronic Resource
    Pollucite- and Leucite-related Phases: A2BX5O12 and ACX2O6 (A = K, Rb, Cs; B = Be, Mg, Fe, Co, Ni, Cu, Zn, Cd; C = B, Al, Ga, Fe, Cr; X = Si, Ge) (1989)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 573 (1989), S. 223-230 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pollucit- und Leucit-verwandte Phasen: A2BX5O12 und ACX2O6 (A = K, Rb, Cs; B = Be, Mg, Fe, Co, Ni, Cu, Zn, Cd; C = B, Al, Ga, Fe, Cr; X = Si, Ge)Darstellung und kristallographische Daten von 29 neuen Phasen dieser Strukturfamilie werden angegeben. Ein Überblick über die gesamte Strukturfamilie, die bis jetzt 59 Phasen enthält, wird gegeben. Die Familie enthält wenigstens sieben Strukturvarianten, von denen zwei die Pollucit-, CsAlSi2O6, und Leucit-, KAlSi2O6, Struktur sind. Beziehungen zwischen der Kationengröße und dem Strukturtyp werden vorgestellt. Ungewöhnliche Variationen in den Größen der Einheitszelle als Funktion der Kationengröße werden diskutiert, und auf die mögliche Bedeutung für das „partially collapsed framework“-Konzept von Taylor und Henderson wird hingewiesen.
    Notes: Synthesis and crystallographic data on 29 new phases in this family are given. A survey of the crystal chemistry of the complete family, containing 59 phases to date, is presented. The family contains at least seven structural variations, two of which are the pollucite, CsAlSi2O6 and leucite, KAlSi2O6 structures. Correlations between cation size and structure type are presented. Unusual variations in unit cell dimensions as a function of cation size are discussed and the possible relevance of the „partially collapsed framework“ concept of Taylor and Henderson indicated.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19895730123
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  • 5
    Electronic Resource
    Electronic Resource
    Selektivität bei der Umsetzung von Carbokationen mit Nucleophilen, 2. Solvolyse-Mechanismen bei 7-Norbornyl-trifluormethansulfonaten (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2557-2560 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selectivity in the Reaction of Carbocations with Nucleophiles, 2. Solvolytic Mechanisms of 7-Norbornyl TrifluoromethanesulfonatesThe reactions of 7,7-bis(trifluoromethylsulfonyloxy)norbornane (4) with several metal cyanides in dipolar aprotic solvents are studied. The results obtained (Table 1) lead to the conclusion that the solvolysis of 7-substituted 7-norbornyl trifluoromethanesulfonates takes place either according to a kc mechanism or with fission of the S — O bond. In no instance is a C — O fission following an SN2 mechanism to be expected. - The selectivity of the reaction of the intermediate carbocations with nucleophiles cannot be explained by means of N+ correlations nor by the reactivity-selectivity relationship, but can be rationalized according to the HSAB principle.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180632
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  • 6
    Electronic Resource
    Electronic Resource
    Über Struktur und Stereoselektivität von 2-Norbornen-7-yl-Radikalen und -Carbenoiden (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 4281-4284 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Structure and Stereoselectivity of 2-Norbornen-7-yl Radicals and CarbenoidsReduction of 7,7-diiodonorbornene (1) with Grignard reagents proceeds via the 7-iodo-2-norbornen-7-yl radical 2. From the observed syn-stereoselectivity, the absence of π-delocalization in 2 is inferred. This result agrees with the existence of an equilibrium mixture of two classical pyramidal structures (2a and 2b), in which the syn-isomer 2a predominates. The reaction of 1 with methyllithium takes place with anti-stereoselectivity; this fact proves that the anti-carbenoid 4b-M is more stable than the syn-isomer.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851181035
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  • 7
    Electronic Resource
    Electronic Resource
    Mechanismus der Reaktion von Trifluormethansulfonsäureanhydrid mit Ketonen: Umsetzung mit Campher (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1282-1288 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mechanism of the Reaction of Trifluoromethanesulfonic Anhydride with Ketones: Reaction with CamphorReaction of camphor (1) with trifluoromethanesulfonic anhydride (Tf2O) in the absence of base yields a mixture of 2,2-bis(trifluoromethylsulfonyloxy)camphane (9), 1,2-bis(trifluoromethylsulfonyloxy)-endo-isocamphane (10), and 2,4-bis(trifluoromethylsulfonyloxy)-endo-isocamphane (11). The ratio of these compounds depends on the reaction temperature. 9, 10, and 11 could not be isolated because, during the final aqueous treatment, they undergo hydrolysis leading to 1, 1-camphenyl triflate (2), and 4-camphenyl triflate (3). In the presence of 2,6-di-tert-butyl-4-methylpyridine (DTBMP) 2 is the main reaction product. The reaction rate is independent of the base concentration. It can be inferred that the base only neutralized the trifluoromethanesulfonic acid (TfOH), without reaction with Tf2O. - Reaction of 2 with TfOH in dichloromethane takes place with addition and Nametkin rearrangement. The ratio of these reactions depends on the reaction temperature. No rearrangement products are obtained in the reaction of 1 with TfOH. The reaction paths for the reaction of 1 with Tf2O are compared with those for other ketones, and some conclusions on the electronic requirements of the Nametkin rearrangement are inferred.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180344
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  • 8
    Electronic Resource
    Electronic Resource
    On the Tautomerism of 2-Phenacyl-4-pyrimidinones and Related Compounds (1989)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 919-924 
    Details
    ISSN: 0009-2940
    Keywords: Pyrimidinones ; Tautomerism ; AM1 calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zur Tautomerie von 2-Phenacyl-4-pyrimidinonen und verwandten Verbindungen3-Methyl-2-phenacyl-4-pyrimidinone 1, 2 werden durch Sulfidkontraktion synthetisiert. Aufgrund der NMR-Daten existieren die Verbindungen ausschließlich in der Benzoylmethylen-Form, sowohl in Lösung als auch als Festkörper. Diese Ergebnisse werden durch AM1-Berechnungen für die Stammverbindung bestätigt. Die Untersuchung des Tautomeren-Gleichgewichts mittels dieser semiempirischen Methode wurde auf andere Fälle von Enaminoketon/Enolimin-Tautomerie erweitert.
    Notes: 3-Methyl-2-phenacyl-4-pyrimidinones 1, 2 have been synthesized using the sulfide contraction. According to the NMR data, the compounds 1, 2 exist exclusively as the benzoylmethylene tautomers a both in solution and in the solid state. AM1 calculations of the parent system are in agreement with the experimental observations. The study of the tautomeric equilibrium by this semiempirical method has been extended to other cases of enamino-ketone/enolimine tautomerism.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19891220521
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  • 9
    Electronic Resource
    Electronic Resource
    Zinc(II), cadmium(II), and mercury(II) halide coordination compounds with 1,8-bis(2-pyridyl)-3,6-dithiaoctane. The crystal and molecular structure of Hg2(C16H20N2S2)Br4 (1988)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 567 (1988), S. 101-110 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Koordinationsverbindungen von Zink (II), Cadmium (II) und Quecksilber(II)-Halogeniden mit 1,8-Di-2-pyridyl-3,6-dithiactan. Kristallstruktur von Hg2(C16H20N2S2)Br4Es werden verschiedene Komplexe von 1,8-Di-2-pyridyl-3,6-dithiaoctan (bpdto) mit MX2 (M = Zn, Cd oder Hg und X = Cl, Br oder I) hergestellt und mittels Elementar-analyse, IR, 1H-NMR und konduktometrischen Messungen untersucht. Die Kristallstruktur von Hg2(bpdto)Br4 wird mit Hilfe von Röntgenbeugungsdaten ermittelt (R = 0,079). Hg2(C16H20N2S2)Br4 kristallisiert monoklin in der Raumgruppe P21/c mit vier Formeleinheiten pro Elementarzelle; Gitterkonstanten a = 14,410(3), b = 6,209(5), c = 14,478(5) Å, β = 113,98(1)°. Im Komplex sind zwei Hg-Atome verzerrt-tetraedrisch koordiniert von je einem S-Atom [Hg—S 2,670(3) Å], einem N-Atom [Hg—N 2,366(8) Å] des verbrückenden Liganden und zwei terminalen Br-Atomen [Hg—Br 2,502(1) und 2,501(2) Å].
    Notes: We describe the synthesis and characterization (by elemental analysis, conductance measurements and 1H NMR and IR spectrometry) of compounds with the general formulae M(bpdto) X2 (M = Zn, X = Cl, Br or I; M = Cd, X = Cl or Br) and M2(bpdto)X4 (M = Cd, X = I; M = Hg, X = Cl, Br or I) (bpdto = 1,8-bis(2-pyridyl)-3,6-dithiaoctane). In addition, the structure of Hg2(bpdto)Br4 was determined by single crystal structure analysis and refined to a conventional R factor of 0.079. Hg2(C16H20N2S2)Br4 crystallized in the monoclinic space group P21/c with a = 14.410(3), b = 6.209(5), c = 14.478(5) Å, β = 113.98(1)° and Z = 4. The molecule was found to have two mercury atoms, each tetrahedrally coordinated to two bromide anions [Hg—Br 2.502(1) and 2,501(2) Å], and to one nitrogen atom [Hg—N 2.366(8) Å] and one sulphur atom [Hg—S 2.670(3) Å] of the ligand molecule, which acted as a bridge between the two metal atoms.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19885670112
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